Holographic interferometry as electrochemical emission spectroscopy of a carbon steel in 5–20 ppm TROS C-70 inhibited seawater

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of a carbon steel in blank seawater and seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, as an electromagnetic method, and by the electrochemical impedance (EI) spectroscopy, as an electronic method. So, the abrupt rate change of the number of the fringe evolutions during corrosion tests, EI spectroscopy, of the carbon steel is called electrochemical emission spectroscopy. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of TROS C-70 corrosion inhibitor using the EI spectroscopy method, at room temperature. The electrochemical-emission spectra of the carbon steel in different solutions represent a detailed picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data, which was obtained from the EI. spectroscopy. Consequently, holographic interferometry is found very useful for monitoring the anodic dissolution behaviors of metals, in which the number of the fringe evolutions of the steel samples can be determined in situ.     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

The transition of spontaneous polymerization of acrylamide to “explosive” regime

Experimental results related to the transition of spontaneous polymerization of acrylamide complexes with metal nitrates to the “explosive” regime at room temperature are presented. It is suggested that the “explosion” has a thermal nature. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 859–861, April, 1997.     

Initiation process of L‐lactide polymerization carried out with zirconium(IV) acetylacetonate

Lactide polymerization using zirconium(IV) acetylacetonate [Zr(acac)₄] as an initiator was investigated. In the reaction between Zr(acac)₄ and the monomer molecule, lactide deprotonation and the release of acetylacetone occurred. The structures of the obtained complexes were analyzed with high‐resolution NMR spectroscopy. A computational method was used to calculate the hypothetical structures. The role of the obtained complexes in the initiation of polymerization and the reaction of chain growth was proposed. The influence of the reaction temperature on the structures of the complexes was investigated. Polylactide chain growth proceeded by an insertion‐coordination mechanism. The polymer chain grew on one ligand, which was formed in advance from a deprotonated lactide. The molecular masses of the obtained polymers were the same as the theoretical masses and were directly proportional to the reaction conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1886–1900, 2004     

Reversible addition–fragmentation transfer (RAFT) copolymerization of methyl methacrylate and styrene in miniemulsion

In the reversible addition–fragmentation transfer (RAFT) copolymerization of two monomers, even with the simple terminal model, there are two kinds of macroradical and two kinds of polymeric RAFT agent with different R groups. Because the structure of the R group could exert a significant influence on the RAFT process, RAFT copolymerization may behave differently from RAFT homopolymerization. The RAFT copolymerization of methyl methacrylate (MMA) and styrene (St) in miniemulsion was investigated. The performance of the RAFT copolymerization of MMA/St in miniemulsion was found to be dependent on the feed monomer compositions. When St is dominant in the feed monomer composition, RAFT copolymerization is well controlled in the whole range of monomer conversion. However, when MMA is dominant, RAFT copolymerization may be, in some cases, out of control in the late stage of copolymerization, and characterized by a fast increase in the polydispersity index (PDI). The RAFT process was found to have little influence on composition evolution during copolymerization. The synthesis of the well‐defined gradient copolymers and poly[St‐b‐(St‐co‐MMA)] block copolymer by RAFT miniemulsion copolymerization was also demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6248–6258, 2004     

Influence of charge distribution on the conformation of neutral polyampholytes

Summary Two polyampholyte copolymers based on sodium-2-acrylamido-2-methylsulfonate (NaAMPS) and methacryloyloxyethyltrimethylammonium chloride (MADQUAT) have been prepared either in homogeneous solution or by an inverse microemulsion polymerization technique. The copolymer microstructure was shown to depend on the method of preparation. The microemulsion polymerization yields copolymers with a monomer sequence distribution not far from random while those obtained by polymerization in solution have a strong tendency to alternation. The aqueous-solution properties of the two samples have been investigated by viscometry. The results show that the charge distribution along the copolymer chain affects considerably its conformation, in good agreement with recent theoretical studies. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994     

NMR Study of the propagation center in the cationic polymerization of N-benzoyl-8-octanelactam. II. Investigation of the propagation center

The nature of the propagation center in the cationic polymerization of N-benzoyl-8-octanelactam initiated by octanoylium hexachlcroantimonate, SbCl₅, and Ph₃CAsF₆ in perdeuterated tetrachloroethane or its mixture with o-dichlorobenzene was studied using ¹H, ¹³C, ¹⁹F, ³¹P, ⁷⁵As, and ¹²¹Sb nuclear magnetic resonance (NMR) of model oligomers and the products of their end-capping with triphenylphosphine. In all cases, the nature of the propagation center has been found to be of an acylium ion pair with an SbCl₆^? or AsF₆^? counterion coordinated with the nearest benzoylamide group and cosolvated by the solvent. © 1994 John Wiley & Sons, Inc.     

CRYSTAL STRUCTURE AND MORPHOLOGY OF NASCENT SAMPLES OF SYMMETRIC AROMATIC POLYESTERS——Ⅱ. POLY(p-PHENYLENE 2,6-NAPHTHALATE)

Confined thin film melt polymerization (CTFMP) of naphthalene chloride/hydroquinone (NCMQ, 1/1, molar)mixtures at polymerization temperatures (T_p) below ca. 300℃ resulted in relatively thick, elongated crystals. Polymerizationof NC/HQ above 300℃ between glass yielded well-formed lamellar crystals ca. 100 A thick. Phase Ⅰ and Ⅱ [001] EDpatterns were obtained for all T_p, the relative amount of phase Ⅰ increasing with T_p. Polymerization of naphthalenedicarboxylic acid/hydroquinione diacetate 1/1 mixtures at high T_p also yielded lamellar crystals that "curled up" off of thesubstrate. When the high temperature CTFMP polymerization was conducted between mica, aggregates of lamellae on-edgedeveloped but epitaxial growth did not occur. Epitaxial growth of lamellae between mica could be obtained, however, byconfined thin film solution polymerization, with both of the latter samples yielding apparently related ED patterns from adifferent unit cell than phase Ⅰ or Ⅱ. Fiber patterns, obtained from sheared samples, indicated considerably greater crystaldisorder than in the nascent crystals. Refinement of the phase Ⅰ unit cell parameters, based on the [001] and [01 1] EDpatterns, with modeling based on Cerius~2, suggests a monoclinic phase Ⅰ unit cell with a = 7.76, b = 5.71, c = 14.99 A, α = γ= 90°, β= 99.7°, ρ = 1.47 g/cm~3, space group P12_1/al.